Biogeochemical Mobility of Contaminants from a Replica Radioactive Waste Trench in Response to Rainfall-Induced Redox Oscillations.

Results of investigations into factors influencing contaminant mobility in a replica trench located adjacent to a legacy radioactive waste site are presented in this study. The trench was filled with nonhazardous iron- and organic matter (OM)-rich components, as well as three contaminant analogues strontium, cesium, and neodymium to examine contaminant behavior. Imposed redox/water-level oscillations, where oxygen-laden rainwater was added to the anoxic trench, resulted in marked biogeochemical changes including the removal of aqueous Fe(II) and circulation of dissolved carbon, along with shifts to microbial communities involved in cycling iron (Gallionella, Sideroxydans) and methane generation (Methylomonas, Methylococcaceae). Contaminant mobility depended upon element speciation and rainfall event intensity. Strontium remained mobile, being readily translocated under hydrological perturbations. Strong ion-exchange reactions and structural incorporation into double-layer clay minerals were likely responsible for greater retention of Cs, which, along with Sr, was unaffected by redox oscillations. Neodymium was initially immobilized within the anoxic trenches, due to either secondary mineral (phosphate) precipitation or via the chemisorption of organic- and carbonate-Nd complexes onto variably charged solid phases. Oxic rainwater intrusions altered Nd mobility via competing effects. Oxidation of Fe(II) led to partial retention of Nd within highly sorbing Fe(III)/OM phases, whereas pH decreases associated with rainwater influxes resulted in a release of adsorbed Nd to solution with both pH and OM presumed to be the key factors controlling Nd attenuation. Collectively, the behavior of simulated contaminants within this replica trench provided unique insights into trench water biogeochemistry and contaminant cycling in a redox oscillatory environment.

Priority issues and key findings from evaluation of disposal records for a legacy radioactive waste site.

This paper reports on a detailed investigation into the disposal procedures and records from the operational period (1960-1968) of the Little Forest Legacy Site (LFLS) in eastern Australia. The aims of the paper are firstly, to highlight the priority issues which are relevant to the radiological assessment of the LFLS, and secondly, to present key lessons that may help to guide future investigations of the records at similar sites. Particular effort was put into assessing the various types of relevant documents and the relationships between them. A specific objective of this work was to evaluate an inventory of the wastes which was reported shortly after the time of disposals. A major finding of the study is that the original actinide inventory for LFLS relied solely on estimates from a limited number of specific records known as 'Scrap Disposal Reports' (SDRs). For example, the estimated amount of plutonium disposed at the LFLS was based on only seven SDR records. Given that there are approximately 50000 buried items, it is possible that other Pu-contaminated items could make a significant additional contribution to the amount of Pu present at the site. For some waste components (e.g. beryllium) the documentation shows that rough estimates of disposal quantities were made, based on the number of disposed Be-contaminated items in each trench. The use of such approximations casts some doubt on the accuracy of the previous inventory of wastes at the site. In addition, the early summaries of radionuclide disposals, which categorized radionuclides into groups according to their radiological hazard, contained significant underestimates of the radionuclide inventory in the most hazardous category (referred to at the time as 'Group I' radionuclides). This was mainly due to the omission of the Pu (which had been recorded on the SDRs) from the Group I inventory, but was also in part because the Group I radionuclide content of disposed sludge drums (from a wastewater treatment plant) was not taken into account for most of the disposal period. Establishing the disposal history and radionuclide inventory at legacy sites is an important pre-requisite to evaluating their radiological impact and developing management options. The detailed investigation of the LFLS records shows the importance of understanding the operational practices of the period and the derivation of the original inventories. These insights should help guide future efforts to better understand disposal histories and inventories at LFLS and elsewhere.

Response of Microbial Community Function to Fluctuating Geochemical Conditions within a Legacy Radioactive Waste Trench Environment.

During the 1960s, small quantities of radioactive materials were codisposed with chemical waste at the Little Forest Legacy Site (Sydney, Australia) in 3-meter-deep, unlined trenches. Chemical and microbial analyses, including functional and taxonomic information derived from shotgun metagenomics, were collected across a 6-week period immediately after a prolonged rainfall event to assess the impact of changing water levels upon the microbial ecology and contaminant mobility. Collectively, results demonstrated that oxygen-laden rainwater rapidly altered the redox balance in the trench water, strongly impacting microbial functioning as well as the radiochemistry. Two contaminants of concern, plutonium and americium, were shown to transition from solid-iron-associated species immediately after the initial rainwater pulse to progressively more soluble moieties as reducing conditions were enhanced. Functional metagenomics revealed the potentially important role that the taxonomically diverse microbial community played in this transition. In particular, aerobes dominated in the first day, followed by an increase of facultative anaerobes/denitrifiers at day 4. Toward the mid-end of the sampling period, the functional and taxonomic profiles depicted an anaerobic community distinguished by a higher representation of dissimilatory sulfate reduction and methanogenesis pathways. Our results have important implications to similar near-surface environmental systems in which redox cycling occurs.IMPORTANCE The role of chemical and microbiological factors in mediating the biogeochemistry of groundwaters from trenches used to dispose of radioactive materials during the 1960s is examined in this study. Specifically, chemical and microbial analyses, including functional and taxonomic information derived from shotgun metagenomics, were collected across a 6-week period immediately after a prolonged rainfall event to assess how changing water levels influence microbial ecology and contaminant mobility. Results demonstrate that oxygen-laden rainwater rapidly altered the redox balance in the trench water, strongly impacting microbial functioning as well as the radiochemistry. Two contaminants of concern, plutonium and americium, were shown to transition from solid-iron-associated species immediately after the initial rainwater pulse to progressively more soluble moieties as reducing conditions were enhanced. Functional metagenomics revealed the important role that the taxonomically diverse microbial community played in this transition. Our results have important implications to similar near-surface environmental systems in which redox cycling occurs.

The Sorption Processes of U(VI) onto SiO2 in the Presence of Phosphate: from Binary Surface Species to Precipitation.

The ternary system containing aqueous U(VI), aqueous phosphate and solid SiO2 was comprehensively investigated using a batch sorption technique, in situ attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopy, time-resolved luminescence spectroscopy (TRLS), and surface complexation modeling (SCM). The batch sorption studies on silica gel (10 g/L) in the pH range 2.5 to 5 showed no significant increase in U(VI) uptake in the presence of phosphate at equimolar concentration of 20 µM, but significant increase in U(VI) uptake was observed for higher phosphate concentrations. In situ infrared and luminescence spectroscopic studies evidence the formation of two binary U(VI) surface species in the absence of phosphate, whereas after prolonged sorption in the presence of phosphate, the formation of a surface precipitate, most likely an autunite-like phase, is strongly suggested. From SCM, excellent fitting results were obtained exclusively considering two binary uranyl surface species and the formation of a solid uranyl phosphate phase. Ternary surface complexes were not needed to explain the data. The results of this study indicate that the sorption of U(VI) on SiO2 in the presence of inorganic phosphate initially involves binary surface-sorption species and evolves toward surface precipitation.

Fate of Plutonium at a Former Nuclear Testing Site in Australia.

A series of the British nuclear tests conducted on mainland Australia between 1953 and 1963 dispersed long-lived radioactivity and nuclear weapons debris including plutonium (Pu), the legacy of which is a long-lasting source of radioactive contamination to the surrounding biosphere. A reliable assessment of the environmental impact of Pu contaminants and their implications for human health requires an understanding of their physical/chemical characteristics at the molecular scale. In this study, we identify the chemical form of the Pu remaining in the local soils at the Taranaki site, one of the former nuclear testing sites at Maralinga, South Australia. We herein reveal direct spectroscopic evidence that the Pu legacy remaining at the site exists as particulates of Pu(IV) oxyhydroxide compounds, a very concentrated and low-soluble form of Pu, which will serve as ongoing radioactive sources far into the future. Gamma-ray spectrometry and X-ray fluorescence analysis on a collected Pu particle indicate that the Pu in the particle originated in the so-called "Minor trials" that involved the dispersal of weapon components by highly explosive chemicals, not in the nuclear explosion tests called "Major trials". A comprehensive analysis of the data acquired from X-ray fluorescence mapping (XFM), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) suggests that the collected Pu particle forms a "core-shell" structure with the Pu(IV) oxyhydroxide core surrounded by an external layer containing Ca, Fe, and U, which further helps us to deduce a possible scenario of the physical/chemical transformation of the original Pu materials dispersed in the semiarid environment at Maralinga more than 50 years ago. These findings also highlight the importance of the comprehensive physical/chemical characterization of Pu contaminants for reliable environmental- and radiotoxicological assessment.

Influence of Dissolved Silicate on Rates of Fe(II) Oxidation.

Increasing concentrations of dissolved silicate progressively retard Fe(II) oxidation kinetics in the circum-neutral pH range 6.0-7.0. As Si:Fe molar ratios increase from 0 to 2, the primary Fe(III) oxidation product transitions from lepidocrocite to a ferrihydrite/silica-ferrihydrite composite. Empirical results, supported by chemical kinetic modeling, indicated that the decreased heterogeneous oxidation rate was not due to differences in absolute Fe(II) sorption between the two solids types or competition for adsorption sites in the presence of silicate. Rather, competitive desorption experiments suggest Fe(II) was associated with more weakly bound, outer-sphere complexes on silica-ferrihydrite compared to lepidocrocite. A reduction in extent of inner-sphere Fe(II) complexation on silica-ferrihydrite confers a decreased ability for Fe(II) to undergo surface-induced hydrolysis via electronic configuration alterations, thereby inhibiting the heterogeneous Fe(II) oxidation mechanism. Water samples from a legacy radioactive waste site (Little Forest, Australia) were shown to exhibit a similar pattern of Fe(II) oxidation retardation derived from elevated silicate concentrations. These findings have important implications for contaminant migration at this site as well as a variety of other groundwater/high silicate containing natural and engineered sites that might undergo iron redox fluctuations.

Reduction of U(VI) by Fe(II) during the Fe(II)-accelerated transformation of ferrihydrite.

X-ray absorption spectroscopy has been used to study the reduction of adsorbed U(VI) during the Fe(II)-accelerated transformation of ferrihydrite to goethite. The fate of U(VI) was examined across a variety of pH values and Fe(II) concentrations, with results suggesting that, in all cases, it was reduced over the course of the Fe(III) phase transformation to a U(V) species incorporated in goethite. A positive correlation between U(VI) reduction and ferrihydrite transformation rate constants implies that U(VI) reduction was driven by the production of goethite under the conditions used in these studies. This interpretation was supported by additional experimental evidence that demonstrated the (fast) reduction of U(VI) to U(V) by Fe(II) in the presence of goethite only. Theoretical redox potential calculations clearly indicate that the reduction of U(VI) by Fe(II) in the presence of goethite is thermodynamically favorable. In contrast, reduction of U(VI) by Fe(II) in the presence of ferrihydrite is largely thermodynamically unfavorable within the range of conditions examined in this study.

Solution speciation of plutonium and Americium at an Australian legacy radioactive waste disposal site.

During the 1960s, radioactive waste containing small amounts of plutonium (Pu) and americium (Am) was disposed in shallow trenches at the Little Forest Burial Ground (LFBG), located near the southern suburbs of Sydney, Australia. Because of periodic saturation and overflowing of the former disposal trenches, Pu and Am have been transferred from the buried wastes into the surrounding surface soils. The presence of readily detected amounts of Pu and Am in the trench waters provides a unique opportunity to study their aqueous speciation under environmentally relevant conditions. This study aims to comprehensively investigate the chemical speciation of Pu and Am in the trench water by combining fluoride coprecipitation, solvent extraction, particle size fractionation, and thermochemical modeling. The predominant oxidation states of dissolved Pu and Am species were found to be Pu(IV) and Am(III), and large proportions of both actinides (Pu, 97.7%; Am, 86.8%) were associated with mobile colloids in the submicron size range. On the basis of this information, possible management options are assessed.

Accelerator mass spectrometry measurements of 233U in groundwater, soil and vegetation at a legacy radioactive waste site.

Low-level radioactive wastes were disposed at the Little Forest Legacy Site (LFLS) near Sydney, Australia between 1960 and 1968. According to the disposal records, 233U contributes a significant portion of the inventory of actinide activity buried in the LFLS trenches. Although the presence of 233U in environmental samples from LFLS has been previously inferred from alpha-spectrometry measurements, it has been difficult to quantify because the 233U and 234U α-peaks are superimposed. Therefore, the amounts of 233U in groundwaters, soils and vegetation from the vicinity of the LFLS were measured using accelerator mass spectrometry (AMS). The AMS results show the presence of 233U in numerous environmental samples, particularly those obtained within, and in the immediate vicinity of, the trenched area. There is evidence for dispersion of 233U in groundwater (possibly mobilised by co-disposed organic liquids), and the data also suggest other sources of 233U contamination in addition to the trench wastes. These may include leakages and spills from waste drums as well as waste burnings, which also occurred at the site. The AMS results confirm the historic information regarding disposal of 233U in the LFLS trenches. The AMS technique has been valuable to ascertain the distribution and environmental behaviour of 233U at the LFLS and the results demonstrate the applicability of AMS for evaluating contamination of 233U at other radioactive waste sites.

Trench 'bathtubbing' and surface plutonium contamination at a legacy radioactive waste site.

Radioactive waste containing a few grams of plutonium (Pu) was disposed between 1960 and 1968 in trenches at the Little Forest Burial Ground (LFBG), near Sydney, Australia. A water sampling point installed in a former trench has enabled the radionuclide content of trench water and the response of the water level to rainfall to be studied. The trench water contains readily measurable Pu activity (~12 Bq/L of (239+240)Pu in 0.45 µm-filtered water), and there is an associated contamination of Pu in surface soils. The highest (239+240)Pu soil activity was 829 Bq/kg in a shallow sample (0-1 cm depth) near the trench sampling point. Away from the trenches, the elevated concentrations of Pu in surface soils extend for tens of meters down-slope. The broader contamination may be partly attributable to dispersion events in the first decade after disposal, after which a layer of soil was added above the trenched area. Since this time, further Pu contamination has occurred near the trench-sampler within this added layer. The water level in the trench-sampler responds quickly to rainfall and intermittently reaches the surface, hence the Pu dispersion is attributed to saturation and overflow of the trenches during extreme rainfall events, referred to as the 'bathtub' effect.

Synthesised and modified zeolite for effective management of beryllium contaminants in aqueous media under different conditions.

The effective management of beryllium (Be) in solution is not well established. In this study, zeolite was synthesised from coal fly ash (CFA) and further modified to enhance Be sorption. Results indicated zeolite NaP1 was effectively synthesised, and cross-linked chitosan was grafted in/on the zeolite structure during modification. The Brunauer, Emmett, and Teller (BET) surface area substantially increased from 1.05 m2/g in CFA to 94.0 m2/g in the synthesised zeolite (SZ). Furthermore, the modified zeolite (MZ) showed improved functionality as a reactive site for Be sorption. A comparative sorption study revealed inferior sorption (11.3 %) and higher desorption (56.1 %) of Be using CFA than the sorption using SZ (93.0 % sorption, 2.9 % desorption) and MZ (93.0 % sorption, 1.5 % desorption). Consequently, SZ and MZ exhibited higher sorption efficacy than commercial zeolite (57.4 %) and other commercial sorbents. At an experimental pH of 5.5 [relevant to the pH of Little Forest Legacy Waste Site (LFLS) soil, a representative site for potential Be contamination], MZ showed higher sorption than SZ. The higher sorption in MZ resulted from its elevated ligand complexation [with nitrogen (N), phosphorous (P), and oxygen (O)] and some ion exchange (with Na+, -NH3+, and H+ ions) mechanisms. Moreover, increased sorption (up to 99 %) was observed using colloidal soil solution (CSS) collected from LFLS soil to simulate field conditions after extensive rainfall. Different environmental factors (e.g. pH, temperature, time, CSS, concentrations of sorbate, and sorbent) regulated Be sorption. The sorption mechanism was best described by the Langmuir model, and the pseudo-second-order kinetic model (R2 = 0.999). Moreover, the sorption reaction was spontaneous (ΔG = -Ve), enthalpically, and entropically influenced. Desorption hysteresis (ndesorption/nsorption < 1) suggested irreversible sorption, and the chemisorption mechanism of Be was confirmed by Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis.

Environmental chemistry response of beryllium to diverse soil-solution conditions at a waste disposal site.

This study evaluated how the variation in different sorption conditions of beryllium (Be) in soil-water systems (electrolytes; ionic strengths; competing, counter, and co-existing ions; concentrations of Be and soil; and temperature) affected Be's environmental behaviour. For this reason, potentially contaminated soil was collected from a legacy waste site near Sydney, Australia. The sorption-desorption plateau for Be was found at >12.5 g L-1 (soil/solution), considering higher sorption and limited desorption. Variable surface charges developed by different added ions (competing ions, counter ions, and co-existence of all ions) were not always correlated with Be sorption. However, effects of added ions in Be sorption (increased by counter ions and decreased by competing ions) primarily occurred at low pH, with no noticeable changes at pH > 6 due to the hydration and precipitation behaviour of Be at higher pH. Both laboratory data and modelling indicated the substantial effect of counter ions on increased sorption of Be. Relatively higher amounts of sorption under the co-existence of all added ions were suggested from synergistic actions. Sorption was favourable (KL > 0, and 0 < RL < 1) across all concentrations and temperatures at pH 5.5, and high retention (84-97%) occurred after four desorption cycles indicated specific sorption. The sorption process was exothermic (ΔH > -43 kJ mole-1), while desorption was endothermic (ΔH > +78.4 kJ mole-1). All sorption-desorption reactions were spontaneous (ΔG = -Ve), and executed without any structural deformation (ΔS = nearly zero) of soil particles. However, the effect of temperature on desorption was influenced by the concentrations of Be. Higher retention and different sorption-desorption parameters (Kd-desorption > Kd-sorption; Kf-desorption > Kf-sorption; ndesorption/nsorption < 1) indicate limited mobility of Be and the presence of desorption hysteresis in the studied soil under the experimental conditions.

Electroacoustic isoelectric point determinations of bauxite refinery residues: different neutralization techniques and minor mineral effects.

Bauxite refinery residue (BRR) is a highly caustic, iron hydroxide-rich byproduct from alumina production. Some chemical treatments of BRR reduce soluble alkalinity and lower residue pH (to values <10) and generate a modified BRR (MBRR). MBRR has excellent acid neutralizing (ANC) and trace-metal adsorption capacities, making it particularly useful in environmental remediation. However, soluble ANC makes standard acid-base isoelectric point (IEP) determination difficult. Consequently, the IEP of a BRR and five MBRR derivatives (sulfuric acid-, carbon dioxide-, seawater-, a hybrid neutralization, i.e, partial CO(2) neutralization followed by seawater, and an activated-seawater-neutralized MBRR) were determined using electroacoustic techniques. Residues showed three significantly different groups of IEPs (p < 0.05) based around the neutralization used. Where the primary mineral assemblage is effectively unchanged, the IEPs were not significantly different from BRR (pH 6.6-6.9). However, neutralizations generating neoformational minerals (alkalinity precipitation) significantly increased the IEP to pH 8.1, whereas activation (a removal of some primary mineralogy) significantly lowered the IEP to pH 6.2. Moreover, surface charging curves show that surfaces remain in the ±30 mV surface charge instability range, which provides an explanation as to why MBRRs remove trace metals and oxyanions over a broad pH range, often simultaneously. Importantly, this work shows that minor mineral components in complex mineral systems may have a disproportionate effect on the observable bulk IEP. Furthermore, this work shows the appropriateness of electroacoustic techniques in investigating samples with significant soluble mineral components (e.g., ANC).

Inhibition of uranium(VI) sorption on titanium dioxide by surface iron(III) species in ferric oxide/titanium dioxide systems.

Uranium (U(VI)) sorption in systems containing titanium dioxide (TiO(2)) and various Fe(III)-oxide phases was investigated in the acidic pH range (pH 2.5-6). Studies were conducted with physical mixtures of TiO(2) and ferrihydrite, TiO(2) with coprecipitated ferrihydrite, and with systems where Fe(III) was mostly present as crystalline Fe(III) oxides. The presence of ferrihydrite resulted in decreased U(VI) sorption relative to the pure TiO(2) systems, particularly below pH 4, an unexpected result given that the presence of another sorbent would be expected to increase U(VI) uptake. In mixtures of TiO(2) and crystalline Fe(III) oxide phases, U(VI) sorption was higher than for the analogous mixtures of TiO(2) with ferrihydrite, and was similar to U(VI) sorption on TiO(2) alone. X-ray absorption spectroscopy of the TiO(2) system with freshly precipitated Fe(III) oxides indicated the presence of an Fe(III) surface phase that inhibits U(VI) sorption-a reaction whereby Fe(III) precipitates as lepidocrocite and/or ferrihydrite effectively blocking surface sorption sites on the underlying TiO(2). Competition between dissolved Fe(III) and U(VI) for sorption sites may also contribute to the observed decrease in U(VI) sorption. The present study demonstrates the complexity of sorption in mixed systems, where the oxide phases do not necessarily behave in an additive manner, and has implications for U(VI) mobility in natural and impacted environments where Fe(III) (oxyhydr)oxides are usually assumed to increase the retention of U(VI).

Role of beryllium in the environment: Insights from specific sorption and precipitation studies under different conditions.

In this study, we examined factors influencing the environmental behaviour of Be, specifically considering soils collected from a legacy radioactive waste disposal site near Sydney (Australia). The precipitation study showed the formation of Be(OH)2 (amorphous) from ICP standard solution, but a mixture of Be(OH)2 (alpha), Be(OH)2 (beta) and ternary Na/S-Be (ΙΙ)-OH(s) solid phase were formed from BeSO4 solutions. The precipitation of Be started at relatively lower pH at higher concentrations than at the lower Be concentration as indicated by both laboratory data and simulation. Across the pH range, the Be sorption curve was divided into three phases, these being pH 3-6, pH 6-10, and pH > 10, within which sorption of Be with soil was 9-97%, 90-97%, and 66-90%, respectively. Beryllium solubility was limited at pH > 7, but a sorption study with soil showed chemisorption under both acidic and alkaline pH (pH 5.5 and 8) conditions, which was confirmed by FTIR and XPS analysis. At pH 5.5 (specifically relevant to the study site), sorption of Be was 72-95%, in which 77% and 46% Be was respectively sorbed by separated fulvic and humic acid fractions. The irreversible chemisorption mechanism was controlled by SOM at higher pH, and by metal oxyhydroxides at lower pH. Both organic and inorganic components synergistically influence the specific chemisorption of Be at the intermediate pH 5.5 of field soil.

Beryllium in contaminated soils: Implication of beryllium bioaccessibility by different exposure pathways.

Inhalation exposure and beryllium (Be) toxicity are well-known, but research on bioaccessibility from soils via different exposure pathways is limited. This study examined soils from a legacy radioactive waste disposal site using in vitro ingestion (Solubility Bioaccessibility Research Consortium [SBRC], physiologically based extraction test [PBET], in vitro gastrointestinal [IVG]), inhalation (simulated epithelial lung fluid [SELF]) and dynamic two-stage bioaccessibility (TBAc) methods, as well as 0.43 M HNO3 extraction. The results showed, 70 ±â€¯4.8%, 56 ±â€¯16.8% and 58 ±â€¯5.7% of total Be were extracted (gastric phase [GP] + intestinal phase [IP]) in the SBRC, PBET, and IVG methods, respectively. Similar bioaccessibility of Be (~18%) in PBET-IP and SELF was due to chelating agents in the extractant. Moreover, TBAc-IP showed higher extraction (20.8 ±â€¯2.0%) in comparison with the single-phase (SBRC-IP) result (4.8 ±â€¯0.23%), suggesting increased Be bioaccessibility and toxicity in the gastrointestinal tract when the contamination derives from the inhalation route. The results suggested Be bioaccessibility depends on solution pH; time of extraction; soil reactive fractions (organic-inorganic); particle size, and the presence of chelating agents in the fluid. This study has significance for understanding Be bioaccessibility via different exposure routes and the application of risk-based management of Be-contaminated sites.

Contaminant release, mixing and microbial fluctuations initiated by infiltrating water within a replica field-scale legacy radioactive waste trench.

Numerous legacy near-surface radioactive waste sites dating from the mid 20th century have yet to be remediated and present a global contamination concern. Typically, there is insufficient understanding of contaminant release and redistribution, with invasive investigations often impractical due to the risk of disturbing the often significantly radiotoxic contaminants. Consequently, a replica waste trench (~5.4 m3), constructed adjacent to a legacy radioactive waste site (Little Forest Legacy Site, LFLS), was used to assist our understanding of the release and mixing processes of neodymium (Nd) - a chemical analogue for plutonium(III) and americium(III), two significant radionuclides in many contaminated environments. In order to clarify the behaviour of contaminants released from buried objects such as waste containers, a steel drum, representative of the hundreds of buried drums within the LFLS, was placed within the trench. Dissolved neodymium nitrate was introduced as a point-source contaminant to the base of the trench, outside the steel drum. Hydrologic conditions were manipulated to simulate natural rainfall intensities with dissolved lithium bromide added as a tracer. Neodymium was primarily retained both at its point of release at the bottom of the trench (>97 %) as well as at a steel container corrosion point, simulated through the emplacement of steel wool. However, over the 8-month field experiment, advective mixing initiated by surface water intrusions rapidly redistributed a small proportion of Nd to shallower waters (~1.5-1.7 %), as well as throughout the buried steel drum. Suspended particulate forms of Nd (>0.2 µm) were measured at all depths in the suboxic trench and were persistent across the entire study. Analyses of the microbial communities showed that their relative abundances and metabolic functions were strongly influenced by the prevailing geochemical conditions as a result of fluctuating water depths associated with rainfall events. The site representing steel corrosion exhibited divergent biogeochemical results with anomalous changes (sharp decrease) observed in both dissolved contaminant concentration as well as microbial diversity and functionality. This research demonstrates that experimental trenches provide a safe and unique method for simulating the behaviour of subsurface radioactive contaminants with results demonstrating the initial retention, partial shallow water redistribution, and stability of particulate form(s) of this radioactive analogue. These results have relevance for appropriate management and remediation strategies for the adjacent legacy site as well as for similar sites across the globe.

Rare earth elements and yttrium as tracers of waste/rock-groundwater interactions.

Increasing concentrations of Rare Earth Elements (REE) plus yttrium (REY) are entering the environment due to human activities. The similar chemical behaviour across the whole REY, i.e. the lanthanide series (lanthanum to lutetium) and yttrium, allows their use as tracers, fingerprinting rock-forming processes and fluid-rock interactions in earth science systems. However, their use in fingerprinting waste and particularly low-level radioactive waste has not received much attention, despite the direct use of REE in the nuclear industry and the traditional use of REE as proxies to understand the environmental mobility of the actinide series (actinium to lawrencium). The highly instrumented low-level radioactive waste site at Little Forest (Australia) allows a detailed REY study, investigating interactions with local strata, neighbouring waste forms and shallow groundwater flows. Groundwater samples and solids from cored materials were recovered from 2007 to 2012 from the study site and regional baseline sites in the same geological materials. The REY in water samples were analysed by automated chelation pre-concentration (SeaFast, ESI) followed by ICP-MS determination, while solid samples were analysed using Neutron Activation Analysis (NAA) and X-ray fluorescence scanning (ITRAX). Solid rocks showed no REY departed from typical Upper Crust compositions in either Little Forest or regional background sites. Shallow groundwater from ~4-5 m, at or slightly below waste trench levels, showed water-waste interaction as a marked enrichment, relative to shale-normalised patterns, in samarium, europium and gadolinium, with depleted yttrium. Leachate samples from the neighbouring urban landfill show different REY normalised patterns. REY distribution changes with depth through increased interaction with shales and sandstones. Variations in pH and redox conditions lead to widespread precipitation of Fe-hydroxides, which scavenge REY with differential uptake by precipitating solids, resulting in increases in Y and higher Y/Ho ratio in the groundwater along the flow path. Our study revealed that the Little Forest low-level radioactive waste has a REY fingerprint different to that of groundwater in surrounding land uses. REY can be used to fingerprint diverse waste sources, assess the mobility of lanthanides inferring the mobility of selected actinides, and to trace the fate of REY during groundwater recharge. The approach presented can refine source allocation and trace pollutant mobility in current and legacy urban, mixed and radioactive waste sites around the world.

Effect of amorphous Fe(III) oxide transformation on the Fe(II)-mediated reduction of U(VI).

It has recently been reported that the Fe(II)-catalyzed crystallization of 2-line ferrihydrite to goethite and magnetite can result in the immobilization of uranium. Although it might be expected that interference of the crystallization process (for example, by the presence of silicate) would prevent uranium immobilization, this has not yet been demonstrated. Here we present results of an X-ray absorption spectroscopy study on the fate of hexavalent uranium (U(VI)) during the Fe(II)-catalyzed transformations of 2-line ferrihydrite and ferrihydrite coprecipitated with silicate (silicate-ferrihydrite). Two-line ferrihydrite transformed monotonically to goethite, whereas silicate-ferrihydrite transformed into a form similar to ferrihydrite synthesized in the absence of silicate. Modeling of U L(III)-edge EXAFS data indicated that both coprecipitated and adsorbed U(VI) were initially associated with ferrihydrite and silicate-ferrihydrite as a mononuclear bidentate surface complex. During the Fe(II)-catalyzed transformation process, U(VI) associated with 2-line ferrihydrite was reduced and partially incorporated into the newly formed goethite mineral structure, most likely as U(V), whereas U(VI) associated with silicate-ferrihydrite was not reduced and remained in a form similar to its initially adsorbed state. Uranium(VI) that was initially adsorbed to silicate-ferrihydrite did, however, become more resistant to reductive dissolution indicating at least a partial reduction in mobility. These results suggest that when the Fe(II)-catalyzed transformation of ferrihydrite-like iron oxyhydroxides is inhibited, at least under conditions similar to those used in these experiments, uranium reduction will not occur.

Uranium sorption on various forms of titanium dioxide--influence of surface area, surface charge, and impurities.

Titanium dioxide (TiO(2)) has often served as a model substrate for experimental sorption studies of environmental contaminants. However, various forms of Ti-oxide have been used, and the different sorption properties of these materials have not been thoroughly studied. We investigated uranium sorption on some thoroughly characterized TiO(2) surfaces with particular attention to the influence of surface area, surface charge, and impurities. The sorption of U(VI) differed significantly between samples. Aggressive pretreatment of one material to remove impurities significantly altered the isoelectric point, determined by an electroacoustic method, but did not significantly impact U sorption. Differences in sorption properties between the various TiO(2) materials were related to the crystallographic form, morphology, surface area, and grain size, rather than to surface impurities or surface charge. In-situ attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopic studies showed that the spectra of the surface species of the TiO(2) samples are not significantly different, suggesting the formation of similar surface complexes. The data provide insights into the effect of different source materials and surface properties on radionuclide sorption.